Certain pyrazoloquinazolone compounds



United States Patent 3,150,136 CERTAIN PYRAZOLOQUINAZOLONE C(PMPOUNDS Gerhard Woifrum, Opladen, Roll Putter, Dusseldorf, and

Karl-Heinz Menzel, Coiogne-l/llulheim, Germany, assignors to Farheufahriken Bayer Alitieugesellschaft, Leverliusen, Germany, a corporation of Germany No Drawing. Filed Jan. 17, 1%1, Ser. No. 83,167 Claims priority, application Germany Sept. 5, H59 9 tllaims. (Cl. 26tl--26.4}

The invention relates to new heterocyclic compounds; it further relates to azo dyestuffs and to their metal complex compounds.

An object of the present invention are are dyestuffs of the general formula R l N and their metal complex compounds. In the formula, A, B, D and E represent hydrogen or various substituents usual in azo dyestuffs which may be identical or different from one anothere.g. halogen and nitro-, acylamino-, alkoxy, carboxylic acid, sulphonic acid, sulphonamide or sulfone groups, R represents hydrogen or an alkyl, aryl, carboxylic acid, carboxylic acid amide or carboxylic acid ester group, X represents a direct linkage or the group represents a metal complex forming group such as OH or COOH or a radical which can be transformed into such a group, such as OCH H, SO H etc. The alkyl or aryl radicals of the substituent R can be further substituted.

The metal complex compounds of the present invention are obtained by metalizing azo dyestuffs of the aforesaid general Formula I in a manner known as such in substance or on the fibre. For this purpose one can proceed for example by reacting dyestuffs of the aforesaid general formula in which Y represents a group capable of complex formation or a grouping capable of being transformed in such a group with salts of copper, chromium, cobalt or nickel. It the reaction with copper salts is carried out in the presence of oxidation agents, there can also be used dyestuffs of the aforesaid formula in which Y represents hydrogen, since in these cases the hydrogen atom is exchanged for a hydroxyl group. As metalizing agent there may also be used complex forming compounds which already contain one chromium atom per dyestuii molecule in complex linkage and which react with one molecule of a metal-free dyestui'i of the Formula I with the formation of mixed 1:2 chromium complex dyestuffs.

Azo dyestufis of the general Formula I can be produced by coupling diazonium compounds of amines of the formula B (H) in which A, B and Y have the above given significance, with pyraZolo-benzimidazoles or pyrazolo-quinazolones. Suitable amines for the preparation of the diazonium compounds are e.g. l-amino-Z-hydrQXy'benZene, l-amino-Z- hydroxy 4 nitro-benzene, l-amino-2-hydroxy 4-chlorobenzene, 3-amino-4-hydroxy benzene-sulphonic acid-(1), 3-arnino-4-hydroxy-S-chloro benzene-sulphonic acid(1),

ice

3-amino-4-hydrozy-benzene sulphonamide--(l), 4-arnino- B-hydroxy benzene sulphonamide-(l), and their derivatives substituted at the sulphonarnide nitrogen by one or two organic radicals, ethyl-(3-amino-4-hydroxy-phenyl) sulfone, amino-hydroquinone Inethylene-sulfone ether, anthranilic acid, sulfoanthranilic acid, anthranilic acid sulfonamide and their derivatives substituted at the amide nitrogen by organic radicals, and furthermore sulfanilic acid, 3-amino-4-methoxy-benzene sulfonamide-( 1) and lamino-Z-chloro-S-nitrobenzene.

Suitable pyrazolo-benzimidazoles or pyrazoloquinazolones are e.g. the following: 3-methylpyrazolo'-' [1,5 l .2]-benzimidazole, 3 -carboxypyrazolo-[1',5': 1,2]- benzimidazole, 3'-methylpyrazolo-[1,5': 1,2] -benzimidazolesulfonic acid (5) or -(6), 3' -rnethylpyrazolo- [1,5: 1,2] 5 methylbenzimidazole, 3'-methylpyrazolo- [1,5: 1,2] benzimidazolesulfonamide (5), 3-methylpyrazolo [5',1:2,3] quinazolone, 3'-carboxypyrazolo- [5, 1' :2,3]-quinazolone, 3'-methylpyrazolo-[5 ',1 2,3 -5- chloroquinazolone, 3 phenylpyrazolo-[5,1':2,3]-quinazolone, 3' methylpyrazolo-[5',1':2,3]-quinazolonesulionic acid (6). The pyrazolo-benzimidazoles can be produced according to the process described in Belgian patent specification 579,898.

The pyrazolo-(l',5':3,2)-quinazolones, which are to be used for the production of dyestufis of the Formula I, are new and likewise an object of the present invention. They correspond to the apparent general formula Therein denote:

R hydrogen, an optionally substituted alkyl radical, an optionally substituted aryl radical, a carboxylic acid group, carboxylic ester or carboxylic acid amide group;

R hydrogen or an optionally substituted alkyl, cycloalkyl or aryl radical;

Ar: an ortho-condensed, monoor polynuclear, optionally substituted aromatic ring system. The pyrazolo-quinazolones of Formula 111 can be produced by reacting aromatic o-amino carboxylic acid hydrazides which carry at the nitrogen of the amino group at least one hydrogen atom, with B-oxo carboxylic acid esters.

From the aromatic o-amino carboxylic acid hydrazides and the fl-oxo carboxylic acid esters there may first result the corresponding hydrazones with splitting oil of a mole of Water, and these in the further course of the reaction are cyclized with splittin off of alcohol or an aromatic hydroxy compound and a second molecule of water, to give the end products. The course of the reaction described is illustrated in the following equations exemplified by the reaction of anthranilic acid hydrazide with acetoacetic acid ethyl ester to give 3-methyl-pyrazolo- (l,5':3,2) quinazolone:

For the production of the compounds of Formula III the starting components are preferably used in equimolar quantities. As reaction medium, according to the solubility of the components, there come into consideration water or organic solvents such as, e.g., methanol, ethanol, glycol monomethyl ether, dimethyl formamide or acetonitrile. It is however also possible to work without a solvent. The reaction, which takes an exothermic course, occurs in general without further application of heat. In some cases the production of the pyrazolo-quinazolones can be carried out in neutral or weakly acid medium; often indeed the second step of the reaction, the cyclization of the hydrazone, proceeds only in the presence of alkalies, such as soda, potash, borax, magnesium oxide or organic bases, which are added to the reaction mixture at the outset or only after formation of the hydrazones.

It is unnecessary to isolate the hydrazones occurring as an intermediate step, which are, moreover, mostly soluble. The process for producing compounds of the Formula III can on the contrary even be carried out in a single operation. At the final stage the often almostquantitative yield of pyrazolo-quinazolone produced is filtered off, washed on the filter first with the solvent used in the reaction and then with hot water, and then dried. The products thus obtained which for the most part contain only slight impurities, are with few exceptions difficultly soluble in most organic solvents, but can be recrystallized, however, from dimethyl formamide, glycol monomethyl ether or a mixture of the latter with pyrrolidone. In many cases the substance can be dissolved in hot aqueous hydrochloric acid, purified with charcoal and then precipitated by addition of sulfates or aromatic sulfonic acids as difiicultly soluble salts, or their solution may be salted out in hot aqueous caustic soda with common salt.

According to the aforesaid process a great number of pyrazolo-quinazolones of the Formula III are easily obtainable, since o aminoaroylhydrazides as well as ,B-oxocarboxylic acid esters are already known in great number in the literature or can be readily produced according to conventional methods. Thus for example there come into consideration for the reaction with B-oxocarboxylic esters the hydrazides of anthrani lic acid, N-alkyl anthranilic acids, 2,3-amino naphthoic acid, N-alkyl-2,3- amino naphthoic acid, and their derivatives substituted one or more times in the aromatic nucleus for example by halogen, alkyl, alkoxy, aryl, phenoxy, amino, acylamino, alkyl amino, carboxyl, sulfonamide, or sulfonic acid groups or if necessary via bridge members by heterocyclic radicals; the following fi-oxocarboxylic acid esters may be used, inter alia, acetoacetic acid ethyl ester, acetoacetic acid phenyl ester, acetoacetic acid cyclohexyl ester, acetoacetic acid benzyl ester, stearolyacetic acid ethyl ester, oxalacetic acid diethyl ester, benzoyl acetic acid ethyl ester or acetone dicarboxylic acid dimethyl ester.

According to the above process it is furthermore possible to obtain heterocyclic compounds with several pyrazolo-quinazolone radicals, by starting from aromatic compounds which contain several amino groups and carboxylic acid hydrazide groups standing in ortho positions thereto, the fi-oxocarboxylic acid esters being added in quantities which are at least equivalent to the amino groups. As starting products there come into consideration, for example, aromatic compounds with several benzene nuclei of which each carries one amino group and a carboxylic acid hydrazide group standing in ortho positions thereto, for example benzidine-o.o'-dicarboxylic acid hydrazide.

The pyrazolo-(l',5:3,2)-quinazolones of the Formula III may be treated with alkylating agents whereupon new N-substituted pyrazolo-(l,5':3,2)-quinazolones of the following structure are obtained which are likewise an object of this invention:

II 0 R2 0 In these formulae Ar, R and R have the above menstituted lower alkyl radical or an aralkyl or cycloalkyl residue and X stands for an anion which is derived from the alkylating agents, such as C11 Br, I CH SO 3 C H SO C H SO (p-tolucnesulfate').

If R denotes H, the nitrogen atoms designated by 1 or 2 are to be considered as the positions of the alkylation reaction. Theposition of introducing the alkyl radical depends on the chosen reaction conditions. In an alkaline solution, i.e. under conditions where a substantial proportion of the pyrazolo-quinazolone is present as anion, the alkylation predominantly occurs at the nitrogen atom designated by 1 (provided R means H). Without the addition of alkalies, however, the alkylating agents yield in organic hydroxyl-group-free solvents at an elevated temperature with the anions deriving from the alkylating agents almost exclusively salts of pyraZolo-quinazolones alkylated at N This behaviour of pyrazolo-quinazolones during alkylation may be illustrated by the following two reaction schemes:

O on,

Chlorobenzene, 120 C.

The salts obtained by alkylation at the nitrogen atom N are readily water-soluble and, if R means H, are converted by the calculated amount of alkali into free water-insoluble pyrazolo-quinalozolones which in turn may be alkylated at the nitrogen atom N in organic hydroXyl-group-free solvents at an elevated temperature. These reactions may be illustrated by the following formulae:

The N-substituted pyrazolo-(1',5':3,2)-quinazolones of the Formulae IV may likewise be employed as intermediates for the preparation of azo dyestuffs, e.g. by introducing a nitroso group into 4-position, reducing the NO-group to NH diazotizing and coupling the 4-diazo compound with a common coupling component.

The metal complex compounds of dyestuffs of the Formula I produced by using the pyrazolo-benzimidazoles As alkylating agents there may be considered comounds of the general formula wherein R denotes an alkyl, substituted alkyl or aralkyl or cycloalkyl radical which may be further substituted by halogen, hydroxyl, alkoxy, dialkylamino, carboxyl, ester, sulfonic acid or sulfone groups, and wherein X stands for a residue which may be split off as anion such as a halogen, the group -O SOR or -OSO R, furthermore for the cyclic sulfuric acid esters of 1,2- and 1,3- diols as well as the cyclic inner esters of hydroxy-sulfonic acids. Finally, ethylenes and ethylene oxides capable of addition may likewise be used for alkylation in an alkaline medium. The following alkylating agents may be mentioned by way of illustration: ethyl iodide, diethyl sulfate, benzene sulfonic acid methyl ester, benzene sulfonic acid cyclohexanol ester, benzyl chloride, diethyl amino ethyl chloride, butane sultone, propane sultone, glycol sulfate and, finally, acrylonitrile, ethylene oxide, propylene oxide and epichlorohydrin.

When alkylating both reactive nitrogen atoms, the same or a different alkylating agent can be used for the second reaction.

As hydroxyl-group-free solvents there may be used for example aromatic or aliphatic hydrocarbons which may be halogenated. When working in a non-alkaline medium, the reaction temperature is preferably 89-180 0, while a temperature of 1() C. to +150 C. is applied when working in an alkaline medium (pH about 8-10).

or pyrazolo-quinazolones are according to the type of substituents present in the dyestuif, readily or slightly soluble or insoluble in water. The metal complex dyestuffs insoluble in water are suitable as pigments, while the water-soluble metal complexes are especially suitable for dyeing animal and polyamide or polyurethane fibres; furthermore they can be fixed in the presence of alkali on cellulose fibres after introduction of reactive groups which are able to undergo chemical reaction with the hydroxyl groups of the cellulose fibre, such as monoor dichlorotriazinyl radicals, monoor dichloro-pyrimidinyl radicals, halogen alkyl or halogen acyl radicals, OSQ H-groups or their alkali metal salts, epoxide groups etc.

The parts given in the following examples are parts by weight. The examples are to illustrate the invention without, however, limiting it thereto.

This application is a continuation-in-part of our copending application Serial No. 53,611 by Karl-Heinz Menzel, Rolf Piitter and Gerhard Wolfrum, assigned to the same assignee, and filed on September 2, 1960.

EXAMPLE 1 18.8 parts of 1-amino-Z-hydroxybenzene sulfonarnide- (5) are dissolved in 75 parts of water and 30 parts of hydrochloric acid (d=l.l9) and diazotized with the addition of ice at 0 C. with 7 parts of sodium nitrite in 15 parts of water. After removal of excess nitrous acid by means of amidosulfonic acid or urea a solution is added to othe diazotization mixture of 17.1 parts of 3-methyl pyrazolo(1,5:l,2)-benzimidazole in 120 parts of 1 N hydrochloric acid and the mixture is run into 45 parts of caustic soda (d=1.46) and 50 parts of ice. After coupling is completed the dyestuff solution is clarified and after heating to 100 C. with good stirring, treated with a solution of 7.5 parts of potassium bichromate and 13.8 parts of glucose in 50 parts of water within minutes. The reaction mixture is held for a short time at 100 C., allowed to cool to 70 C., and the resulting 2:1 chromium complex of the dyestuff of the formula N 110- I l 1 1 SO NT-I AF N CHa is separated by addition of sodium chloride, filtered off and dried. The ground powder obtained dissolves in water with red colour and dyes wool from an acetic acid bath in clear bluish red shades of good fastness properties.

The same chromium complex dyestuff is obtained if in the production of the metal free dyestufl, in place of the l-amino-Z-hydroxy benzene sulfonarnide-(S) there is used as diazo component 1-amino-2-methoxy benzene sulfonamide-(S) and the monoazo dyestuff obtained is demethylated in chroming according to known processes (compare e.g. French patent specification 1,083,204) e.g. with chromium formate in ethylene glycol or formamide at 140 C.

For the production of the cobalt complex dyestuff the solution obtained in the coupling of the monoazo dyestuff is heated to 80 C. and treated with 115 parts of the cobalt-containing solution described in the following. When dried the cobalt complex dyestuff is a dark brown powder which dissolves in water with a red colour; Wool is dyed from an acetic acid bath in brick red shades with good fastness.

The cobalt-containing solution used was prepared in the following manner;

A solution of 281 parts of crystalline cobalt sulfate in 1000 parts of water was treated with strong stirring with 500 parts of a of aqueous ammonia solution; air was then blown through sufficiently long until a sample upon the addition of a 10% caustic soda solution gave no further precipitate. Finally the mixture was made up to 2000 parts with Water.

EXAMPLE 2 18.8 parts of 1-amino-2-hydroxy-benzene sulfonamide- (4) are coupled in the manner described in Example 1 with 3-methylpyrazolo-(1',5':1,2)-benzimidazole to give the azo dyestuif of the formula The azo dyestulf is then chromed with potassium bichromate and glucose. The chromium complex thus obtained is an almost black powder when dry which dissolves in water with a bluish red shade and dyes wool from a Weakly acid bath in bluish bordeaux shades of good fastness properties.

The cobalt complex obtainable in an analogous manner according to the cobalting process of Example 1 is a brown powder which dissolves in water with a bluish red shade and dyes Wool from a weak acid bath in clear bordeaux shades of good fastness properties.

8 EXAMPLE 3 l if is separated by the addition of sodium chloride. It is a brown red powder when dry.

Wool is now dyed with this dyestuif in an acid bath at C. in orange-yellow shades. The dyeing liquor is then treated with a potassium bichromate solution and heated for about another 45 minutes. The shade of colour thereby changes to a clear red of good fastness properties due to the formation of the chromium complex.

EXAMPLE 4 18.9 parts of 1-amino-2-hydroxy-benzene sulfonic acid- (5) are diazotized in the usual way. The di-azotization mixture is then added at 0 C. to a solution of 20.1 parts of pyrazolo-( 1,5 1,2)-benzimidazole-carboxylic acid- (3) in 150 parts of water and 65 parts of caustic soda solution (d=1.46). When coupling is completed the reaction solution is buffered with acetic acid and the dyestutf of the formula is separated by the addition of sodium chloride. When dry it represents a brick red powder.

Wool is dyed with this dyestufi? in an acid bath at 100 C. in orange shades. The dyebath is then treated with a potassium bichromate solution and heated for about 45 minutes. A bordeaux dyeing is obtained of good fastness properties.

EXAMPLE 5 21.7 parts of S-sulfo-anthranilic acid are dissolved in 18 0 parts of Water and 18 parts of a caustic soda solution (d:1.46) and after addition of 7 parts of sodium nitrite, treated in 25 parts of water and about 50 parts of ice with 35 parts of hydrochloric acid (d=l.19). After removing excess nitrous acid by means of amido sulfonic acid or urea a solution is added to the diazotization mixture of 17.1 parts of 3'-methyl-pyrazolo-(l,5:1,2)-benzimidazole in parts of 1 N hydrochloric acid and the mixture is allowed to run into 275 parts of a 20% soda solution at 0-5 C. When coupling is completed the azo dyestuff formed of the formula is precipitated by the addition of common salt.

Wool is dyed with this dyestutf in an acid bath at 100 C. in yellow shades. The dye bath is then treated with a potassium bichromate solution and heated for about 45 minutes. An orange-yellow dyeing is then obtained with good fastness properties.

EXAMPLE 6 18. 8 parts of 1-amino-2-hydroxy-benzene sulfonamide-(5) are dissolved in 75 parts of water and 30 parts of hydrochloric acid (d=1.19) and diazotized with the addition of ice at C. This diazotization mixture is then added to a solution of 19.9 parts of 3-methylpyrazolo-( 1,5' 3,2) -quinazolone in 120 parts of methanol, 15 parts of a caustic soda solution (d=1.46) and 30 parts of a 25% ammonia solution, whereby, by addition of ice, the temperature is maintained below 5 C. After coupling is completed the azo dyestutf formed of the formula is separated by the addition of salt and then filtered on. For the production of the chromium complex the dyestufi is dissolved hot in 300 parts of water and 24 parts of a caustic soda solution (d=1.46) and the solution is boiled under refiux after the addition of 70 parts of a solution of chrome oxalic acid sodium salt which possesses a chromium content of 2.3%, for 7 hours. The chromium complex dyestuif thus formed is separated by the addition of sodium chloride, then filtered off and dried. It is a black-brown powder which dissolves in water with a violet color and dyes wool from a weakly acid bath in violet shades of good fastness properties, especially outstanding light fastness.

The cobalt complex which can be obtained from the metal free dyestuff of this example by the method described in Example 1, is a red-brown powder which dissolves in water with a bluish-red shade and dyes wool from a weakly acid bath in fast bordeaux shades.

EXAMPLE 7 22.3 parts of 1-amino-2-hydroxy-3-chloro-benzene sulfonic acid-(5) are diazotized in the usual way and the diazotization mixture is then added to a solution of 19.9 parts of 3-methyl-pyrazolo-(1',5':3,2)-quinazolone in 120 parts of methanol, parts of a caustic soda solution (d=1.46) and 30 parts of a 25% ammonia solution, the temperature being held below 5 C. by the addition of ice. After coupling is complete, the azo dyestuff formed of the formula is separated by the addition of common salt and filtered elf.

Wool is dyed with this dyestuif in an acid bath at 100 C. in orange-red shades. The dye bath is then treated with a potassium bichromate solution and heated for about 45 minutes. The shade of color changes towards bordeaux. The dyeing possesses good fastness properties.

1 0 EXAMPLE 8 23.7 parts of l-amino-2-hydroxy-benzene disulfonic acid-(3,5) are diazotized in the usual Way and the diazotization mixture is then added to a solution of 25.3 parts of 3'-methyl-pyrazolo-(1',5':3,2)-7-amino quinazolone in a mixture of 175 parts of methanol, 15 parts of a caustic soda solution (d=l.46) and 30 parts of a 25% ammonia solution, the temperature being held below 5 C. by the addition of ice. After coupling has finished, the azo dyestutf formed is separated off by the addition of salt and then filtered oif.

For production of the copper complex the dyestulf is dissolved in 300 parts of water with the addition of soda to give a weakly alkaline reaction and the solution is then slowly added to another solution of 25 parts of crystalline copper sulfate, 15 parts of glacial acetic acid and 260 parts of Water, warmed. to 50 C. After the addition of salt the copper complex dyestuif formed is filtered off. It dissolves in water at neutral reaction with a bluish-red color.

If the copper sulfate is replaced, in an otherwise similar manner of operation, by 29 parts of crystalline nickel sulfate, the nickel complex dyestuif is obtained, soluble in water with red color.

The metal complex dyestuffs described in this example can be further modified by reactions at the amino group. For example if the copper complex dyestuff is dissolved at a neutral to weakly acid reaction in water and, after addition of a small quantity of a dispersing agent, 18.5 parts of cyanuric chloride are added at 0-5 C. while simultaneously treating with soda in accordance with the splitting off of hydrochloric acid, the copper complex is obtained of the dyestuff of the formula SiOQH N=-N SOQH H H Y l I CH3 N N N o N u Cl C This dyestuff can be fixed in known manner on cotton by reaction with the fibre in the presence of alkali.

EXAMPLE 9 18.8 parts of 1-amino-Z-hydroxy-benzene sulfonamide-(5) are diazotized as described in Example 1 and the diazotization mixture is added at 0 C. to a solution of 24.3 parts of 3-methyl-pyrazolo-(1,5:3,2) quinazolone carboxylic acid-(8) in 300 parts of water and 18 parts of a caustic soda solution (d=1.46), treated with 30 parts of soda. When the coupling is complete, the azo dyestutf formed is separated off by the addition of sodium chloride and then filtered off. The dyestuif is then dissolved in 350 parts of hot water with the addition of 15 parts of soda and the solution treated at -100 C. within 15 minutes with a solution of 15 parts of potassium bichromate and 27.6 parts of glucose in parts of water. The 1:1 chromium complex dyestuit thus obtained of the formula is precipitated by the addition of sodium chloride and neutralization with acetic acid and then filtered off. When dried it is a red powder which dissolves in water with a red color and dyes wool from a weakly acid bath in clear red shades of outstanding fastness to light.

EXAMPLE l 3'-Methyl-Pyraz0l0- (1 ',5: 3,2 -Quinaz0l0ne 37.75 grams mol) of anthranilic acid hydrazide and 32.5 grams 4 mol) acetoacetic acid ethyl ester are stirred at room temperature in 100 ml. methanol. The temperature slowly rises 810 C. and the anthranilic acid hydrazide goes completely into solution. After one hour it is treated with 25 grams of anhydrous soda whereupon a renewed rise of temperature is immediately to be observed; by immersing the reaction vessel in cold water the mixture is maintained at 35--40 C. until after about /2 hour the mixture solidifies to a thick, no longer stirrable crystal pulp. It is allowed to stand for a further 2 hours and filtered. The residue is washed on the suction filter with 100 ml. of warm methanol at 50 C. and then with 200 ml. of hot water. For further purification of the still weakly grey-green colored crystal mass it is dissolved at the boil in 300 ml. water and 80 ml. hydrochloric acid (d=1.19), clarified once or twice with some charcoal until the solution is colorless and it is then treated with the hot solution of 85 grams of naphthalene-1,5-disulfonic acid sodium salt in 200 ml. of water. The naphthalene disulfonate of the pyrazolo-quinazolone separates soon in crystalline form. It is allowed to cool and filtered. For the production of the free pyrazolo-quinazolone, the salt is heated in 1 liter of water and gradually treated with a caustic soda solution until neutral. After filtering off with suction and drying the pure white product melts at 365370 C. with decomposition. Yield: 39 grams.

C H N O[l99.2].-Calc.: C, 66.32; H, 4.55; N, 21.10; 0, 8.03. Found: C, 66.10; H, 4.71; N, 21.09; 0, 8.26.

EXAMPLE 1 1 The product of Example 10 is also obtainable when 37.75 grams of anthranilic acid hydrazide, 32.5 grams of acetoacetic acid ethyl ester and 25 grams of anhydrous soda are simultaneously introduced into 1 00 ml. of methanol at room temperature. The mixture warms immediately and is maintained at the beginning by immersing in cold water at 35-40 C. After 1%. hours the material solidifies to a thick crystal pulp. The working up and purification are carried out in the same way as described in Example 10.

EXAMPLE l2 3'-methyl-pyrazolo-(1',5:3,2)-quinazolone will likewise be obtained by the following process:

To a mixture of 50 grams of phenol and 0.5 ml. of a caustic soda solution there are slowly added dropwise 21 grams of freshly distilled diketene and the temperature maintained by immersing the reaction vessel in cold water, at 40-45 C. At the end it is cooled to 25 C., treated with 10.0 ml. of methanol and 37.75 grams (0.25 mol) of anthranilic acid hydrazide are introduced. The mixture gradually warms up and is maintained by external cooling at 35 C. The anthranilic acid hydrazide goes at first into solution; after about 45 minutes a fresh precipitate crystallizes out and after 90 minutes the content of the vessel solidifies to a stiff crystal pulp. This is allowed to stand for hours at room temperature and then filtered off. The perfectly white residue is taken up in 200 ml. of methanol, heated to boiling, whereby the pyrazolo-quinazolone remains undissolved, and filtered. The product melts, after drying, at 365-370 C. (decomposition). Yield: 42 grams.

A similar result is achieved if acetoacetic acid phenyl ester, obtained from the reaction of phenol with diketene and still containing sodium phenolate is treated with 2 ml. of glacial acetic acid before the addition of the hydrazide and in otherwise similar manner, or if instead of methanol, benzene is used as reaction medium.

EXAMPLE 13 37.75 grams (0.25 mol) of anthranilic acid hydrazide are finely distributed in 100 ml. of water and added at 20 C. to the reaction product of phenol with 21 grams of diketone treated with 2 ml. of glacial acetic acid (see Example 12). With rapid stirring the anthranilic acid hydrazide migrates immediately into the non-aqueous layer consisting of acetoacetic acid phenyl ester and phenol, which after about 20 minutes solidifies, to disintegrate in fine white crystals after a further 15 minutes. Simultaneously, the temperature rises to 45 C. To complete the reaction, the product is maintained for a further 2 hours at 45 C. and subsequently treated with 65 ml. of a caustic soda solution, 300 ml. of water and after 5 minutes with grams of common salt. After cooling to 10 C., the reaction product which is present as the sodium salt in fine pale yellow crystals, is filtered off and washed on the filter with a 20% salt solution. The residue is then stirred in hot Water adjusted to neutral re action with hydrochloric acid, filtered oil and dried. Yield: 42 grams.

EXAMPLE 14 2 grams of 3'-methyl-pyrazolo-(l',5:3,2)-quinazolone are dissolved with 1.5 ml. of a caustic soda solution (d=1.48) in 50 ml. of water and, after the addition of 10 ml. of a 20% soda solution, treated with the diazonium salt prepared in the usual way from 1.8 grams of p-sulphanilic acid. The azo dyestutf formed is salted out and filtered off. It dyes wool from an acid bath in yellow shades.

EXAMPLE 15 3 -M e thyl-Pyrazolo- (1 ',5 ':3 ,2 -5-Chl0r0-Quinaz0l0ne 46.6 grams (0.25 mol) of 6-chloro-2-amino benzoic acid hydrazide and 32.5 grams (0.25 mol) of acetoacetic acid ethyl ester are stirred at room temperature in 200 ml. of methanol. After the hydrazide has dissolved within a few hours, it is treated with 25 grams of soda and stirred for 48 hours at room temperature. After this time a thick crystal pulp is present which is filtered oh and Washed with methanol and hot water. For further purification it is dissolved in 1 liter of water with 11 ml. of a caustic soda (d=l.48), clarified and treated dropwise in the hot with about 200 ml. of a 20% common salt solution. The product separates as the sodium salt in fine yellow needles. It is filtered and washed with a 5% common salt solution. The residue is heated in 800 ml. of water and treated with hydrochloric acid to give a neutral reaction. The 3-methyl-pyrazolo-(l,5: 3,2)-5-chloroquinazolone separates out as a fine white precipitate which. is filtered off and dried. Melting point=360370 C. (decomposition). Yield: 36 grams.

C H CIN O [234.66].-Cal.: C, 56.30; H, 3.87; N, 17.91; Cl, 15.11. Found: C, 56.03; H, 3.44; N, 17.64; Cl, 15.41.

The 6-chloro-2-amino benzoic acid hydrazide used in this reaction, melting point=163164 C. was produced, starting from 6-chloro-amino benzoic acid, by preparing first chloro-isatoic anhydride from it in hydrochloric acid solution with phosgene and then reacting this with excess hydrazine hydrate.

EXAMPLE 16 3 '-Methyl-Pyraz0l0- (1 ',5'.'3 ,2 -7-Amin0-Quinaz0l0ne 41.5 grams (0.25 mole) of 2,4-diamino benzoic acid hydrazide and 32.5 grams of acetoacetic acid ethyl ester are stirred at room temperature in ml. of methanol. The temperature gradually rises to 810 C. As soon as a clear solution is present it is treated with 25 grams of l3 soda whereupon a further rise of temperature is to be observed; by immersing the reaction vessel in cold water, heating of the material above 40" C. is avoided. After about /2 hour the separation of the reaction product begins which is present after 1 hour as a no longer stirrable crystal pulp. It is allowed to stand for a further 2 hours and filtered. The greenish colored residue is heated with 200 ml. water and filtered. It is then dissolved at 80 C. in 2 liters of water and 100 ml. of hydrochloric acid, treated with charcoal, filtered and the filtrate neutralized with soda. The precipitate is filtered off, washed with Water and dried. Yield: 36 grams; melting point 360363 C. (decomposition).

C H N O [214.22].--Calc.: C, 61.67; H, 4.71; N, 26.16. Found: C, 61.29; H, 4.98; N, 26.20.

For producing the diamino benzoic acid hydrazide, 4- nitro-2aminobenzoic acid ethyl ester is hydrogenated in tetrahydrofuran in the presence of a nickel catalyst at 35 C. The 2,4-diamino benzoic acid ester obtained is reacted in ethylene glycol at 110 C. with hydrazine hydrate. The 2,4-diamino benzoic acid hydrazide thus obtained melts at 205-206 C.

EXAMPLE 17 21 grams of diketene are reacted according to the instructions of Example 12 with phenol and, after dilution with 100 ml. of methanol, 57.5 grams (0.25 mol) of 2- amino-S-sulfamyl-benzoic acid hydrazide are added thereto and the mixture stirred for 24 hours. It is then filtered off and the precipitate washed first With methanol and then with water. For purification or" the crude product it is dissolved in 300 ml. of a 7% aqueous ammonia solution, filtered after the addition of some charcoal and again precipitated by addition of 40 grams of ammonium bicarbonate. Yield: grams; the product does not melt up to 385 C.

C H N 0 S [287.28].Calc.: C, 47.47; H, 3.62; N, 20.14. Found: C, 47.40; H, 3.65; N, 20.14.

EXAMPLE 18 3 '-Phenyl-Pyraz0l0- (1 ',5 :3,2 -Quim1z0lone 37.75 grams (0.25 mol) of anthranilic acid hydrazide and 48 grams (0.25 mol) of benzoylacetic acid ethyl ester are stirred at room temperature in 200 ml. methanol. After 24 hours a clear solution is present which is treated with 25 grams of soda. The temperature rises within one hour from 25 C.- C. After 24 hours the reaction product is filtered olf, washed with methanol and water, dried and recrystallized from 1200 ml. of glycol monomethyl ether. Yield: 15 grams; melting point 337 338 C.

C1GH11N3O C, H, N, 16.09. Found: C, 73.54; H, 4.46; N, 15.90.

EXAMPLE l9 3 '-Methyl-Pyraz0l0- (1 ',5 13,2 -6,7-Benz0quinaz0l one 56.75 grams (0.25 mol) of 3-amino-B-naphthoic acid hydrazide and 32.5 grams (0.25 mol) of acetoacetic acid ethyl ester are stirred in 200 ml. of methanol. The pale yellow hydrazide gradually goes over into the deep-yellow colored, likewise diflicultly soluble, hydrazine. After 4 hours it is treated with 25 grams of soda. At first a strong brightening is observed. The next morning the material solidifies to a thick crystal pulp of the yellow reaction product. It is filtered and Washed with methanol and water. For further purification the very difiicultly soluble residue is boiled in 200 ml. of methanol. Yield: 39 grams. The product decomposes at 335340 C. with dark coloration.

C H N O [249.26].Calc.: C, 72.27; H, 4.45; N, 16.86. Found: C, 72.65; H, 4.65; N, 16.52.

i4 EXAMPLE 20 Pyraz0l0-(1,5:3,2)-Quinaz0l0ne Acetic Acid Methyl Ester-(3) To a slurry of 37.8 grams /4 mol) of anthranilic acid hydrazide in ml. of methanol, 50.5 grams 4 mol) of acetone dicarboxylic acid diethyl ester are added with stirring at room temperature. After about 1 hour the anthranilic acid hydrazide has gone completely into solution, the temperature having risen to about 10 C. The acyl hydrazone formed begins to crystallize out of the solution and after a further hour the material consists of a thick crystal pulp. 15 grams of anhydrous soda are then added and stirring is continued until no further reaction heat is freed. The reaction mixture is then cooled to 0 10 C. and the reaction product isolated by filtering oft under suction. By re-esterification of the reaction product with the methanol contained in the reaction mixture 50 grams of a lightly yellow colored pyrazolo- (1,5':3,2)-quinazolone acetic acid methyl ester-(3) are obtained. The compound crystallizes from methanol in colorless felted needles and melts at 255 C. with decomposition.

C H N O [257.2].Ca1c.: C, 60.69; H, 4.31; N, 16.34; 0, 18.66. Found: C, 60.76; H, 4.22; N, 16.12; 0, 18.71.

EXAMPLE 21 grams (=1 mol) of 2-methyl amino-benzoic acid hydrazide are slurried in 200 ml. of methanol and 130 grams (=1 mol) of acetoacetic acid ethyl ester are added with stirring at room temperature. With a temperature rise from 20 C. to about 40 C. the Z-methylamino-ben- Zoic acid hydrazide completely goes into solution in the course of 1-2 hours. The clear brown solution which now contains the acyl hydrazone is then treated with 53 grams of anhydrous soda. The cyclization which is now carried out proceeds likewise exothermically and the temperature of the reaction mixture is maintained for 23 hours without external application of heat or cooling at 3040 C. When the temperature begins to fall below 30 C. the reaction has ended. The mixture is diluted with 400 to 500 ml. of ice water, the reaction product filtered off with suction and washed Well with Water. 188 grams (:88% of the theoretical) are obtained of a lightly yellow colored crude product. After recrystallization from methanol the compound is completely colorless and melts at 243-244 C. The compound gives a slightlysoluble hydrochloride crystallizing as colorless fielted needles.

C12I'111N39 [213.2].Calc.: C, 67.60; H, 5.20; N, 19.70; 0, 7.50. Found: C, 67.93; H, 5.11; N, 19.64; 0, 7.86.

EXAMPLE 22 3'-Methyl-Pyraz0l0-(1 ',5 :3,2)-6-Acetylamin0- Quinazolone 56 grams (0.25 mol) of 2-amino-5-acetylamino benzoic acid hydrazide and 32.5 grams of acetoacetic acid ethyl ester are stirred in 100 ml. of methanol until a clear solution is present. This is then treated with 25 grams of soda. The solution immediately becomes green in color and the temperature gradually rises for about 10 C. and after about 1 hour the reaction product crystallizes out. It is filtered, washed first with methanol and then with hot Water and dried. The yield amounts to 38 grams. The product may be recrystallized from dimethyl formamide (1 gram dissolves in 20 ml). The substance does not melt up to 380 C.

C H N O [256.26].-Calc.: C, 60.93; H, 4.72; N, 21.87. Found: C, 61.12; H, 5.08; N, 21.83.

For production of Z-amino-5-acetylamino-benzoic acid hydrazide, 2-amino-5-acetylamino-benzoic acid is first dissolved in water 4 mol in 2 liters) with hydrochloric acid and transformed into the substituted isatoic acid anhy- 15 dride with phosgene, which is subsequently reacted with hydrazine hydrate.

EXAMPLE 23 34'-Dimethyl-Pyraz0l0- (1 ',5 :3,2 -Quinazl0ne 37.75 grams A mol) of anthranilic acid hydrazide and 36 grams mol) of a-methylacetoacetic acid ethyl ester are stirred at room temperature in 100 ml. of methanol, until a clear solution is present and then over a period of 2 hours treated with 4 portions each of mol of trirnethyl amine in methanol solution. After 24 hours it is treated with ml. of glacial acetic acid and 10 ml. of water and after hour the precipitate is filtered ofi. The weakly reddish colored product is dissolved in 300 ml. of water and 50 ml. of hydrochloric acid (d=l.19) while hot, treated with charcoal and filtered. By neutralization of the almost colorless filtrate the reaction product is separated in a crystalline form, melting point 325 C. (decomposition; above 280 C. the color of the substance gradually becomes deep red).

C H N O[213.23].Calc. C, 67.59; H, 5.20; N, N, 19.71. Found: C, 67.63; H, 5.20; N, 19.80.

EXAMPLE 24 32M ethyl-Pyrazolo- (1 ',5 :3 ,2 -7-Nitr0 -Q ujnazol one 21 grams of diketene are reacted according to the instructions of Example 12 with phenol, acidified with 2 ml. of glacial acetic 'acid, diluted with 100 ml. of dimethyl formamide and there are finally added 49.75 grams of 4- nitro-2-amino benzoic acid hydrazide (melting point 227-230 C. produced from the ester with hydrazine hydrate in ethylene glycol at 110 C). The hydrazide gradually goes into solution. After 2 hours a very slow separation of fine yellow crystals is observed. The material is then warmed for 5 hours to 40 C. After cooling to C. the reaction product is filtered off, washed on the filter first with a little dimethyl formamide then 3 times with 100 ml. methanol and dried. Yield: 20 grams. For further purification the product can be recrystallized from dimethyl formamide. At about 310 C. the substance decomposes without melting.

C H N O [244.21].Calc.: C, 54.10; H, 3.30; N, 22.94. Found: C, 54.46; H, 3.08; N, 22.90.

EXAMPLE Pyrazol0-(1',5':3,2)-Quinaz0l0ne:Carb0xylic Acid Ethyl Ester-(3) 37.8 grams mol) of anthranilic acid hydrazide and 47 grams mol) of oxalacetic acid diethyl ester are stirred in 150 ml. of methanol until complete solution of the anthranilic acid hydrazide. The temperature thereby rises for about 8-10 C. As soon as a clear solution is formed it is treated with 25 grams of anhydrous soda, whereupon a fresh temperature rise is observed. Heating of the reaction mixture above -45 C. is avoided by immersing the reaction vessel in cold water. When the temperature begins to fall below 30 C. the reaction has finished. The reaction product is isolated by filtering off under suction. It is washed once with methanol and again with water. The yield of pyrazolo-(1,5:3,2)- quinazolone-carboxylic acid ethyl ester-(3) amounts to about 70% of the theoretical. The compound forms after recrystallizing from a great quantity of methanol, almost colorless crystals and decomposes with brown coloration at 2751280" C.

EXAMPLE 26 3'-Methyl-Pyraz0l0-(1,523,2 -Quinaz0l0ne Carboxylic' Acid-(7) obtained from 50 grams of phenol and 21 grams of diketene. The hydrazide is immediately taken up in the non-aqueous layer which, with temperature rise, takes on a deep yellow coloration and solidifies to thick crumbs. It is held for a further 2 hours at 45 C. whereby the reaction mass gradually brightens to pale yellow and finally disintegrates into fine crystals and is treated instantly with 70 ml. of a caustic soda solution. At first a clear deep yellow solution is obtained from which, however, after a few seconds the reaction product crystallizes out (as the sodium salt). It is treated again with 25 grams of common salt, cooled to 0 C. and the precipitate filtered off. After stirring in hot water and addition of hydrochloric acid to give a weak acid reaction the free carboxylic acid is obtained. Yield: 35 grams. The product does not melt up to 360 C.

C H N O [243.22].-Calc.: C, 59.26; H, 3.73; N,

17.28. Found: C, 59.10; H, 3.98; N, 17.45.

EXAMPLE 27 1-Phenyl-3'-Methyl-Pyraz0l0-(1 ,5' :3,2 -Quinazolone To the mixture of acetoacetic acid phenyl ester and phenol obtained from 50 grams of phenol and 21 grams of diketenetsee Example 12), ml. of methanol and 2 ml. of glacial acetic acid are added. At room temperature and with stirring 56.8 grams of diphenylamino carboxylic acid-(2)-hydrazide are introduced. With increase of temperature the hydrazide gradually goes into solution. When the whole is dissolved clearly it is heated for a further hour to 35-40 C. and then cooled by placing on ice at 0 C. The reaction product crystallizes out of the solution and can be filtered off. By washing with methanol it is freed from the associated phenol. The yield amounts to 35 grams. The l-phenyl-3-methylpyrazolo-(1',5:3,2)-quinazolone melts at 243-245 C.

C H N O [275.3].Calc.: C, 74.17; H, 4.76; N, 15.27; 0, 5.81. Found: C, 74.51; H, 4.66; N, 15.34; 0, 6.02. a

The pyrazolo-quinazolones mostly melt considerably above 300 C. Since at this temperature a notable decomposition already occurs, the melting points given in the examples were established in such a manner that in the approximately indicated region after each temperature rise of 5 C. a fresh sample was brought into the copper block used.

EXAMPLE 28 38 grams of anthranilic acid hydrazide are slurried in 100 ml. of methanol and 43 grams of cyclohexanone-(2)- carboxylic acid ethyl ester-(1) are added. After 2 hours stirring at room temperature a clear solution is present into which 15 grams of anhydrous soda are sprinkled. Stirring is continued for a further 4 hours at room temperature and 2 hours at 40 C. For working up it is diluted with 300400 ml. of water, rendered weakly acid with diluted hydrochloric acid (pH 5-6 and the separated reaction product filtered olf under suction. The reaction product is washed with water and methanol. After drying 35 grams are obtained of a weak yellow colored compound, which may be recrystallized well from dimethyl formamide and decomposes above 300 C. with dark coloration. The compound has the following constitution:

C H H O [239.26].Calc.: C, 70.28; H, 5.47; N; 17.56; 0, 6.69. Found: C, 70.18; H, 5.28; N, 17.48; 0, 6.88.

17 EXAMPLE 29 42 grams of N-methyl-anthranilic acid hydrazide are reacted with 43 grams of cyclohexanone (2)-carboxylic acid ethyl ester exactly as described in Example 28 and worked up. 33 grams are obtained of a weakly yellow colored compound of melting point 239241 C. The substance has the following constitution:

C H N O [253.29].-Calc.: C, 71.12; H, 5.97; N, 16.59. Found: C, 71.23; H, 6.07; N, 16.55.

EXAMPLE 30 3-Methyl-Pyraz0lo-( 1 ',5 :3,2 -Quinazolone Carboxylic Acid- (8) 44 grams (0.25 mol) of 2-amino-1,3-benzene dicarboxylic acid hydrazide-( 1) are finely powdered and added to the reaction of phenol with 21 grams of diketene (see Example 12) treated with 1.8 ml. of glacial acetic acid. The temperature rises to about 31 C. To end the reaction, the reaction mixture is heated for a further 4 hours to 40 C. The yellow precipitate is filtered ofi under suction after cooling and boiled to remove the phenol, with methanol and benzene. 49 grams (80% of the theoretical) are obtained of a weakly yellow compound with the following constitution:

The substance does not melt up to 350 C.

For the production of 2-arnino-1,3-benzene dicarboxylic acid hydrazide-(l) the corresponding amino dicarboxylic acid is treated with phosgene in bicarbonate alkaline solution and the isatoic acid anhydride thus formed is reacted with excess hydrazine hydrate. The mono-hydrazidc melts at 247250 C. with decomposition.

EXAMPLE 31 3'-Meth -'l-Pyrazolo-(1 ,5:3,2 -Quinazolo'ne-Sulfonic Acid-(6) 54 grams (0.25 mol) of 2-amino-benzoic acid sulfonic acid-( are dissolved in 500 ml. of water with 10 grams of sodium hydroxide. Phosgene is introduced into the solution with water cooling until no further amine can be detected. One part of isatoic acid anhydride precipitates under treatment with phosgene. A further quantity may be isolated by salting out with 125 grams of common salt. The reaction product is introduced with cooling into 35 ml. of hydrazine hydrate and then heated to 100 C. After cooling the hydrazide precipitates.

21 grams of diketene are reacted according to the instructions of Example 12 with phenol and after dilution with water the above described hydrazide is introduced. After 24 hours stirring it is filtered off under suction and the quinazolone heated for purification three times in 150 ml. water and 15 ml. hydrochloric acid. Yield: 41 grams (59% of the theoretical) calculated on the employed Z-amino benzoic acid sulfonic acid-(5). The product does not melt up to 360 C.

1 8 EXAMPLE '32 74.5 grams (0.25 mol) of benzidine-o-dicarboxylic acid-dihydrazide are reacted with acetoacetic acid phenyl ester, from phenol and 50 grams of diketene (analogous to the description of Example 12), and then heated for 4 hours to 40 C. The crystalline precipitate is filtered off under suction and transformed for purification into the hydrochloride with 500 ml. of semi-concentrated hydrochloric acid in the hot. The free pyrazolo-quinazolone is obtained from the salt by heating in 1.5 liters of water. The last traces of phenol may be removed by boiling out with methanol.

Yield: 63 grams (64% of the theoretical) of a compound of the following constitution:

hydrazine hydrate. EXAMPLE 33 22.8 parts of 1,3 dimethyl 4' amino pyrazolo- (l',5:3,2)-quinazolone are dissolved in parts of water and 25 parts of hydrochloric acid (d=1.19) and diazotized with the addition of ice at 0 C. The diaZo solution thus obtained is poured into a solution of 24.5 parts of 2-amino-8-hydroxy-naphthalene sulfonic acid- (6) in 500 parts of water and 25 parts of hydrochloric acid (d=1.19) at 35--40 C. The coupling solution was adjusted by the addition of sodium acetate to a pH value of about 3. After the coupling is complete the azo dye' stuff formed of the formula is filtered oil and dried. It is a brown red powder which dissolves in water with a blue red color and dyes wool from an acid bath in bluish red shades of good fastness properties.

EXAMPLE 34 49.8 g. mol) of 3'-methylpyrazolo-[1',5':3,2]- quinazolone are dissolved in one liter of 50% methanol with a solution of 17 g. of sodium hydroxide in 50 ml. of water. 55 g. of dimethyl sulfate are then added dropwise with vigorous stirring at 20-40 C. within 1-1' /z hours. When the whole of the dimethyl sulfate has been added, the mixture is after-stirred at 40 C. for an hour. The solution should remain alkaline until the end of the reaction. The material is then cooled to 0 C. and the reaction product isolated by filtration. 40 g. of a crude product of the constitution CCHa which, after reduction to the amino compound has a yellow color and melts at 255-256 C. The amine is diazotizable and yields as diazo compound with 1-hydroxy-6- aminonaphthalene-3-sulfonic acid an orange azo dyestuff.

A similar dyestuif is obtainable if diazotized l-amino- 8-hydroXynaphthalene-3,6-sulfonic acid is coupled .with the 3',1-dimethyl-pyrazolo-(1',5':3,2)-quinazolone at the 4'-standing C-atom.

EXAMPLE 3 5 T o a solution of 20 g. of sodium hydroxide in a mixture of 300 ml. of glycol monomethyl ether and 100 ml. of water are added 99.5 g. /2 mol) of 3-methyl-pyrazolo-(1,5:3,2)-quinazolone and the mixture is stirred until clear. 80 g. of diethylamino ethyl chloride are then added to this solution which is heated to the boil for 5 hours. A further 30 g. of diethylamino ethyl chloride are then added and the mixture is heated to the boil for another two hours. After cooling, 500 ml. of a sodium hydroxide solution are added and the mixture is stirred at 0 C. for an hour. The precipitated compound is isolated by filtration and washed with water until alkali-free. After drying, 100 g. of a crude product is obtained melting at 100-110 C. which, after two recrystallizations from 50% methanol, melts at 114-115 C. The compound again precipitates crystals from the melt at melting point temperature and completely solidifies in this new crystal form after a prolonged period. These newly formed crystals have a melting point of 122-124 C. The compound has the constitution C-CH C H N O [298.38].-Cal.: C, 68.43; H, 7.43; N, 18.78; 0, 5.36. Found: C, 68.43, 68.50; H, 7,29, 7.31; N, 18.72, 18.77; 0, 5.75.

EXAMPLE 36 99.5 g. of 3'-methylpyrazolo-[1',5':3,2]-quinazolone are suspended in 400 ml. of chlorobenzene and heated to 120 C. while stirring. 63 g. of dimethyl sulfate are added dropwise at this temperature within /z hour. The reaction is exothermic, the temperature being kept at 120- 125 C. by temporary shutting off the heat. When almost the whole dimethyl sulfate has been added, a clear brown solution is obtained. When the total amount of dimethyl sulfate has been added, stirring is continued at 120 C. for a further 1 to 2 hours. Thereby, the reaction product crystallizes out. After completion of the reaction, the reaction product is cooled to 0 C., filtered off with suction, washed with benzene and dried. 161 g. of a colorless easily water-soluble compound of the following constitution:

onaosoa are thus obtained.

The compound melts at 199-200 C. when introduced into a copper block pre-heated to 190 C.

c n o s [325.33].-Cal.: c, 47.99; H, 4.65; N, 12.92; 0, 24.59; S, 9.86. Found: C, 47.99; H, 4.55; N, 12.84; 0, 24.71; S, 10.00.

EXAMPLE 37 33 g. of the compound described in Example 36 are dissolved in 5 00 ml. of water and a 10% sodium hydroxide solution is added dropwise at 5-20" C., until a constant pH value of about 8 is reached. (Consumption: 39-41 ml. of 10% hydroxide solution.) The precipitated compound is filtered off with suction, washed repeatedly with water and dried. 20 g. of a pale yellow compound are obtained having a melting point of 172-173 C. and the following constitution:

C H N O [213.23].-Cal.: C, 67.59; H, 5.20; N, 19.71; 0, 7.50. Found: C, 67.35; H, 5.27; N, 19.70; 0, 8.09.

If this compound is reacted at the active CH group in the 3'-position with an aldehyde compound, for example in alcohol, and with pyridine as catalyst tothe corresponding azomethine dyestuif, orange to blue dyestuffs are obtained.

With p-dimethylamino-benzaldehyde, this compound yields a blue-red methine dyestuff of the formula EXAMPLE 38 21.3 g. of the compound described in Example 37 are heated in 200 ml. of chlorobenzene to C. while stirring. The compound thereby dissolves. 12.6 g. of dimethyl sulphate are then added dropwise and the mixture is stirred at 100-110 C. for an hour. The bulk of the reaction product crystallizes out at 100 C. After termination of the reaction, the product is cooled to 0 C., filtered 011 and the residue thoroughly washed with water. After drying, 34 g. of a colorless substance of melting point 201-2025 C. are obtained. The compound has the following constitution:

( creosot C14H17N305S [339.36].-Ca1.: C, 49.55; H, 5.05; N,

12.38; 0, 23.57; S, 9.45. Found: C, 49.50; H, 5.11; N, 12.26; 0, 23.79; S, 9.45.

The compound yields with p-dimethylamino-benzaldehyde an intense orange-colored methine dyestutf of the formula EXAMPLE 39 21.3 g. of 1,3-dimethylpyrazolo [1',5:3,2]-quinazolone are heated in 150 ml. of chlorobenzene to 100-110 C. while stirring and 12.6 g. dimethyl sulfate are added dropwise at this temperature. When the whole dimethyl sulphate has been added, the mixture is stirred at 100- 110 C. for another hour and then worked up similarly to the instructions given in Example 36. 31 g. of a colorless readily water-soluble compound are thus obtained which after recrystallization from methanol melts at 200202 C. The compound has the constitution onaoso and is identical with the compound obtained in a different way in Example 38 with regard to all its chemical and physical properties.

C1H17N305S C, H, N, 12.38; 0, 23.57; S, 9.45. Found: C, 49.45; H, 4.93; N, 12.66; 0, 23.19; S, 9.40.

EXAMPLE 40 53.2 g. of the compound described in Example 37 are heated to 100 C. in 100 ml. of chlorobenzene and a solution of 50 g. of p-toluene-sulfonic acid ethyl ester is added dropwise to the clear solution. When the whole material has been added, the mixture is stirred at 120- 130 C. for an hour an dthen worked up similarly to the instructions given in Example 36. 82 g. of a colorless compound are thus obtained which has the following constitution:

After recrystallization from ethanol, the substance melts at ZOO-200.5 C.

C H N O S [413.47].-Cal.: C, 61.00; H, 5.61; O, 15.48; N, 10.16; S, 7.75. Found: C, 61.10; H, 5.31; O, 15.57; N, 10.25; S, 7.90.

EXAMPLE 41 50 g. of 3'-methylpyrazolo-[1',5':3,2]-quinazolone are reacted in 200 ml. of o-dichlorobenzene with 50 g. of p-toluene-sulfonic acid ethyl ester at 160170 'C. Working up of the experimental mixture in carried out similarly to the instructions given in Example 36. 82 g. of a colorless water-soluble compound are thus obtained which 22 after recrystallization from ethanol melts at 221-222 C. and has the following constitution:

EXAMPLE 42 28 g. of 1-phenyl-3'-methylpyrazolo-[1,5:3,21-quinazolone are reacted in 200 ml. of chlorobenzene with 20 g. of p-toluene-sulfonic acid methyl ester at 120130 C. and the mixture is Worked up similarly to the instructions given in Example 36. 44 g. of a very readily water and alcohol-soluble compound are thus obtained having the following constitution:

N on l ll i The compound melts at 186-188 C.

EXAMPLE 43 n i 0 CH3 EXAMPLE 44 g. of 3'- nethylpyrazole-[1,5':3,2]-quinazolone are heated together with 250 g. of acrylonitrile and l-2 g. of a 40% methanolic solution of benzyl-trimethyl ammonium hydroxide to 80 C. while stirring. The progress of the reaction can be easily followed, for example by paper chromatography. After about 2%. hours, the addition of acrylonitrile is terminated. The reaction mixture is allowed to cool while stirring and the reaction product isolated by filtering off with suction. It is washed twice with methanol and, after drying, weighs g. The compound can be recrystallized from dimethyl formamide, it melts at 257259 C. with decomposition and re-solidifies immediately. The addition of acrylonitrile can also be carried out in benzene.

Instead of benzyl-trimethyl ammonium hydroxide there may also be used potassium hydroxide, for example. The resulting compound has the following constitution:

CHzCHzCN and 1 OH 0 Ar l C-R, X- J C N l, 1

wherein R is a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxycarbonylmethyl, phenyl, carboXyl, and carbo-loweralkoxy; R is lower alkyl; R is a member selected from the group consisting of hydrogen, lower alkyl, cyano-lower-alkyl, dilower-alkylamino-lower alkylene, benzyl and phenyl; X is an anion of an alkylating agent; and Ar is an orthocondensed aromatic ring selected from the class consisting of phenylene, sulfophenylene, carboxyphenylene, nitrophenylene, acetylamino-phenylene, sulfonamido-substituted phenylene, chlorophenylene, aminophenylene, naphthylene and 2. A compound of the formula 3. A compound of the formula Q 4. A compound of the formula 5. A compound of the formula f 01- I on,

H CH3 0 6. A compound of the formula 7. A compound of the formula 8. A compound of the formula u U M 9. A compound of the formula References Cited in the file of this patent UNITED STATES PATENTS Kellog Apr. 22, 1952 Enders Mar. 31, 1959 Enders Apr. 21, 1959 Hitchings et al May 17, 1960 

1. A PYRAZOLO-(1'',5'':3,2)-QUINZOLONE SELECTED FROM THE GROUP CONSISTING OF A COMPOUND OF THE FORMULA: 